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UNITED r STATES PATEN T urn-ice nsncrion rnonuc'r Ann raocnss Herman A. Humor: and Lloyd W.

Covert, Philldelphia, Pa assigmi rzto ltiihm it Has. Commay, Philadelphia,

No'Dr-awing. I 1924, Serial No.

.acsasss.

(Mm application October 27,

750,278, new Patent No. Divided and this application March 14, 1936, Serial No. cases a Glaflms. (CL ass-4) This invention relates to new synthetic resins and deals more specifically with resins obtained irom perhvdro derivatives of polynuolear polyhy dric phenols, s'aidperhydro derivatives having the 6 general iormulax no-a-d-a-on 10 wherein R, is a nuclearly hydrogenated aromatic hydrocarbon nucleus, and X and X, each represent a hydrogen atom, alkyl or hydroaromatic hydrocarbon radical, or jointly a polymethylene ns. According to the present invention, the perhydro derivatives of p,pbis-(p-hydrowphenyl) -pro-' pane, bis-(p-hydroxyphenyl) -methane, ram-bis (p-hydroxyphenyl) -ethane, 1,1-bis-(p-hydroxyphenyl) -cyclohexane, bis- (B-hydromaphthmgo methane, p,p-bis(4-hydroxy-3-methylphenyl)- propane, and of similarly constituted compounds, .when heated to temperatures above their melting point but below their critical cracking temperature, preferably in vacu and preferably in the absence of inorganic dehydrating or dehydrogenating catalysts or of phenolic impltrltiesr-gradually lose their crystalline characteristics and go over into hard, transparent, glass-like resins hav-. ing an extremely light color, (generally water These new resins are very resistant to are in general soluble in alcohols such as butanol,

but insoluble in hydrocarbons. In physical prop-* erties these new resins resemble natural dammar .35 resin, giving low viscosity solutions which deposit fast-drying, low solvent retention films of good adhesion, gloss, and hardness. They can be used as resin ingredients "in coating compositions, particularly in cellulose ester or cellulose ether 40 lacquers and in molding powders. They give clear, transparent films alone or when used as resin components in nitrocellulose or cellulose acetate lacquers, and can be used as an intermediate layer when plasticlzed, in the manufacture of so- 46 called safety glass" or non-shatterable glass.

resins such as rosin, copals, ester gums, phenolicformaldehydeand urea-formaldehyde resins.

Another embodiment of the present invention 50 consists in heating the perhydro derivatives having the above general formula, with organic polycarboxylic or monocarboxylic acids or their anhydrides or mixtures thereof, whereby hard, brittle resins or semi-solid balsam-like amorphous bodies are formed, which, depending upon the with natural or synthetic nature of the acids used, may be employed either in the manufacture of oleoresinous varnishes or as plasticizers for organic plastic materials.

The perhydro derivatives herein mentioned as the initial starting materials for-resin manufacture are obtained by hydrogenating polyhydric phenols oi the formulawherein R. is an aromatic hydrocarbon nucleus and! and X represent hydrogen, alkyl, aryl, or jointly a polymethylene ring; in the presence of an inert solvent such as ethyl alcohol'and an active hydrogenation catalyst such as finely divided nickel at about 2009*6. and about atmcspheres pressure until the aromatic groups R are both completely hydrogenated. The perhydro derivatives used are entirely free from partially hyd enated or unhydroge'nated phenolic materials. This is ascertained by removing a sample and testing for solubility in 10% potassium hydroxide solution which dissolves such impurities but does not dissolite the perhydro compound. The temperature of the hydrogenation should not be high enough to crack the starting materials or the finished product; a. temperature range of -220" C. being in general-desirable. The catalyst is then filtered oi! and the solvent is removed by distillation from the phenol-free reacat 200" 10. for 4 hours in its own weight of ethyl alcohol in the presence 01' an active nickel catalyst until 12 atoms of hydrogen have been taken up,v

was heated at 250400 C. for '3-4 hours while maintaining 2 mm. pressure. About 20 grams of residue on cooling formed balsam-like material distilled off. The a colorless,'transparent resin having a melting point of about 160 C. It may be distilled in vacuo with slight decomposition, and boils at about 200 C/2 mm. The vacuum distilled product meltedat 130-150 C. and formed a colorless, hard, brittle, glassy solid. It was soluble in ethyl or butyl alcohol.

In a similar manner, the perhydro derivativ of bis- (p-hydroxyphenyl) -methane.

- HO-CsHp-CHr-CsHsOH, and of m -bis-(p-hydroxyphenyl) -ethane HO-CQHf-CHCI 4OH,

yield colorless resins having similar properties when heated to temperatures of from 250450" C. The higher molecular homologues such as the perhydro derivative of 1,1-bis-(p-hydroxyphenyl) -cyclohexane Hr likewise yield similar resins.

In practicing another embodiment of the present invention, the above mentioned perhydro derivatives either in the crystalline form or in the amorphous resinous condition as obtained by the heat treatment described above, are condensed with organic monocarboxylic or poiycarboxylic acids or with mixtures of monoand polycarboxvlic acids, or anhydrides thereof. The condensation may be carried out by heating either in an inert organic solvent under reflux under conditions whereby the water is continuously, removed as fast as formed, or else in kettles fitted with a short air condenser and constant agitation.

Among the acids which have been found suitable for condensation with the above mentioned perhydro bodies are the fatty acids, particularly propionic, crotonic, lactic, glycollic and a-hya colorless droxyisdbutyric. Other acids such as oleic, linoleic, stearic, cleostearic, ricinoleic or naphthenic can also be used. These latter condensation products are oily or soft somewhat viscous balsam-like masses which are soluble in ethyl acetate and can be usedas plasticizers in coating compositions such as cellulose esters or cellulose ethers. By using rosin or. polycarboxylic acids or anhydrldes such as phthalic, succinic, maleic or adipic, hard resins are obtained upon heating to 190 C.-250 C., with the above mentioned perhydro derivatives. Esteriflcation catalysts such as mineral acids, oxides, during the condensation such as sulphuric, borlc; or phosphoric acids, zinc or calcium oxides, or zinc chloride. Fatty glycerides such as linseed oil, cotton seed oil, tung oil, castor oil, palm oil, soya bean oil and the like may be added during the condensation in order to modify the physical properties of the resins formed.

Example 2. -A mixture of 50 grams perhydrop. 9- [bis- (p-hydroxyphenyl) -propanel' of melting point 192-193 C., and 60 grams propionic anhydrlde was heated at 100 C. for 5-6 hours andthen boiled one hour longer under reflux. The propionic' acid was distilled off and the oily residue distilled in vacuo. It formed a very viscous colorless oil boiling at 200-205 C.ll.5 This preferably under or salts can be present xylene solution heating p lyhydric alcohols product was found to be an excellent plasticizer for nitrocellulose, and cellulose acetate.

Emmple 3.-A mixture of 50. grams'perhydrop,p-[bis-(p-hydroxyphenyl) -propanel, 50 grams lactic acid and 200 com. xylene was refluxed, while using an automatic water separator to continuously remove the water as fast as formed and to return the xylene to the reaction vessel. when no more water came over (3-4 hours) the of the reaction product obtained was cooled, washed thoroughly with-water to remove any free acidity, and the xylene distilled oil. The residue was a pale yellow semi-solid, sticky, balsam-like material which is useful as a plasticizer for phenol-formaldehyde resins. Example 4.-A mixture of 200 grams perhydrofi,fl- [bis-(p-hydroxyphenyl) -propane] and 40 grams maleic anhydride was heated in an open vessel with stirring at l-200 C. for 5 hours. The product obtained was a very pale ambercolored, hard, brittle resin having a melting point 85-90 C. and acid number 1-3. It was readily soluble in toluene. A varnish was prepared from the resin by heating with its own weight of China-wood oil to 600 1". The clear varnish obtained was diluted with its own volume of petroleum naphtha, driers added in the usual manner and a pale, fast-drying varnish obtained. By increasing the amount oi. maleic anhydride to 60 grams and heating as above for 6% hours, a resin having a melting point 111-130 C. was obtained.

Example 5.-A mixtureof 20 grams sebacic acid and 23.8 grams perhydro-p,p- [bis-(p-hydroxyphenyl) -propanel 'was heated in -an open flask at -195 C. for somewhat hard, amber-colored resin was obtained; It was readily soluble in toluene, acetone, or butyl acetate and can be used in nitro cellulose lacquers as a gum.

Emmple 6.-By using 14.8 grams phthalic anhydrlde in place of the sebacic acid in Example 5, and heating at 200 C.- for 7 hours, a colorless, lmrd, brittle resin was obtained, which was readily soluble in butyl acetate, toluene, or warm tung oil.

It is a known that resins are obtained by such as phthalic, maleic, succinic, sebacic and the like. when dihydric' alcohols are used in such prior process, low melting oily or waxy materials are invariably produced. According to the present' invention, however,.condensation products of perhydro derivatives of I with polybasicacids yields hard, brittle, high melting resins which wthe unique property of being readilysoluble in hot drying or semi-drying oils in contrast to the usual alkyd 'ril 5 hours. A very tough,

with poiybasic acids the type set forth herein type resins which must iirst be heated with lon chain. fatty acids or oil-soluble. I

This application is a division of our copending. application Serial No. 150,278 flied. October2'l, 1934 Patent No. 2,068,034.v

We claim: I 1. In a process for preparing a resin the step which consists of heating a material which conrosin in order to become 00 sists of perhydro derivatives of compounds-of the formula v I x no-n-d-n-on,

wherein R is an aromatic hydrocarbon nucleus, 8 and I represent hydrogen, alkyl, aryl, or

ical cracking temperatures; until their crystalline character disappears.

2. In a process for preparing a resin or balsam- 1 like material the step which consists'of heating a material which consists oi a perhydro derivative of a diarylol methane compoundto a temperature above its melting point but below its critical cracking temperature, until its crystalline character disappears.

3. In a process for preparing a resin or balsam-- like material the step which consists of heating a material which consists of a pet-hydro derivative of a diphenylol methane compound to a temperature above its melting point but'below its critical cracking temperature, until its crystalline character disappears.

4. In a process for preparing a resin the step which consists of heating a consists of perhydro-p,p-[bls-(p-hydroxyphenyl)- propane], until its crystalline character disappears.

5. A resin consisting of a material which conz 3 sists of perhvdro derivatives 0! compounds of the formula x no-n- -c-n-on wherein R is an aromatic hydrocarbon nucleus,

X and x' represent hydrogen, alkyl, aryl, or

jointly a poiymethylene ring, which have been heated until their crystalline character is lost.

6. A resin consisting of the product obtained by heating a material which consists of a perhy dro'derivative of adiarylol methane compound until its crystalline character disappears.

'7. A .resi'n consisting of the product obtained by heating a material which consists of a perhydro diphenyioi methane compound until its crystaiiine character disappears.

8, Aresin consisting oi the product obtained by heating a material which consists of perhyarc-pa [bis- (p-hydroxyphenyl) -propane] until its crystalline character disappears.

HERMAN A. BRUSON. LLOYD W. COVERT. I 

